Hydrocarbon conversion using molecular sieve SSZ-56

ABSTRACT

The present invention relates to new crystalline molecular sieve SSZ-56 prepared using a N,N-diethyl-2-methyldecahydroquinolinium cation as a structure directing agent, methods for synthesizing SSZ-56 and processes employing SSZ-56 in a catalyst.

This application claims the benefit of U.S. Provisional Application Ser.No. 60/694,029, filed Jun. 23, 2005.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to new crystalline molecular sieve SSZ-56,a method for preparing SSZ-56 using aN,N-diethyl-2-methyldecahydroquinolinium cation as a structure directingagent and the use of SSZ-56 in catalysts for, e.g., hydrocarbonconversion reactions.

2. State of the Art

Because of their unique sieving characteristics, as well as theircatalytic properties, crystalline molecular sieves and zeolites areespecially useful in applications such as hydrocarbon conversion, gasdrying and separation. Although many different crystalline molecularsieves have been disclosed, there is a continuing need for new zeoliteswith desirable properties for gas separation and drying, hydrocarbon andchemical conversions, and other applications. New zeolites may containnovel internal pore architectures, providing enhanced selectivities inthese processes.

Crystalline aluminosilicates are usually prepared from aqueous reactionmixtures containing alkali or alkaline earth metal oxides, silica, andalumina. Crystalline borosilicates are usually prepared under similarreaction conditions except that boron is used in place of aluminum. Byvarying the synthesis conditions and the composition of the reactionmixture, different zeolites can often be formed.

SUMMARY OF THE INVENTION

The present invention is directed to a family of crystalline molecularsieves with unique properties, referred to herein as “molecular sieveSSZ-56” or simply “SSZ-56”. Preferably, SSZ-56 is in its silicate,aluminosilicate, titanosilicate, vanadosilicate or borosilicate form.The term “silicate” refers to a molecular sieve having a high mole ratioof silicon oxide relative to aluminum oxide, preferably a mole ratiogreater than 100, including molecular sieves comprised entirely ofsilicon oxide. As used herein, the term “aluminosilicate” refers to amolecular sieve containing both aluminum oxide and silicon oxide and theterm “borosilicate” refers to a molecular sieve containing oxides ofboth boron and silicon.

In accordance with the present invention there is provided a process forconverting hydrocarbons comprising contacting a hydrocarbonaceous feedat hydrocarbon converting conditions with a catalyst comprising themolecular sieve of this invention. The molecular sieve may bepredominantly in the hydrogen form. It may also be substantially free ofacidity. The invention includes such a process wherein the molecularsieve has a mole ratio greater than about 15 of (1) silicon oxide to (2)an oxide selected from aluminum oxide, gallium oxide, iron oxide, boronoxide, titanium oxide, indium oxide and mixtures thereof, and has, aftercalcination, the X-ray diffraction lines of Table 2.

Further provided by the present invention is a hydrocracking processcomprising contacting a hydrocarbon feedstock under hydrocrackingconditions with a catalyst comprising the molecular sieve of thisinvention, preferably predominantly in the hydrogen form.

This invention also includes a dewaxing process comprising contacting ahydrocarbon feedstock under dewaxing conditions with a catalystcomprising the molecular sieve of this invention, preferablypredominantly in the hydrogen form.

The present invention also includes a process for improving theviscosity index of a dewaxed product of waxy hydrocarbon feedscomprising contacting the waxy hydrocarbon feed under isomerizationdewaxing conditions with a catalyst comprising the molecular sieve ofthis invention, preferably predominantly in the hydrogen form.

The present invention further includes a process for producing a C₂₀₊lube oil from a C₂₀₊ olefin feed comprising isomerizing said olefin feedunder isomerization conditions over a catalyst comprising the molecularsieve of this invention. The molecular sieve may be predominantly in thehydrogen form. The catalyst may contain at least one Group VIII metal.

In accordance with this invention, there is also provided a process forcatalytically dewaxing a hydrocarbon oil feedstock boiling above about350° F. (177° C.) and containing straight chain and slightly branchedchain hydrocarbons comprising contacting said hydrocarbon oil feedstockin the presence of added hydrogen gas at a hydrogen pressure of about15-3000 psi (0.103-20.7 MPa) with a catalyst comprising the molecularsieve of this invention, preferably predominantly in the hydrogen form.The catalyst may contain at least one Group VIII metal. The catalyst maybe a layered catalyst comprising a first layer comprising the molecularsieve of this invention, and a second layer comprising analuminosilicate zeolite which is more shape selective than the molecularsieve of said first layer. The first layer may contain at least oneGroup VIII metal.

Also included in the present invention is a process for preparing alubricating oil which comprises hydrocracking in a hydrocracking zone ahydrocarbonaceous feedstock to obtain an effluent comprising ahydrocracked oil, and catalytically dewaxing said effluent comprisinghydrocracked oil at a temperature of at least about 400° F. (204° C.)and at a pressure of from about 15 psig to about 3000 psig (0.103 - 20.7Mpa gauge)in the presence of added hydrogen gas with a catalystcomprising the molecular sieve of this invention. The molecular sievemay be predominantly in the hydrogen form. The catalyst may contain atleast one Group VIII metal.

Further included in this invention is a process for isomerizationdewaxing a raffinate comprising contacting said raffinate in thepresence of added hydrogen with a catalyst comprising the molecularsieve of this invention. The raffinate may be bright stock, and themolecular sieve may be predominantly in the hydrogen form. The catalystmay contain at least one Group VIII metal.

Also included in this invention is a process for increasing the octaneof a hydrocarbon feedstock to produce a product having an increasedaromatics content comprising contacting a hydrocarbonaceous feedstockwhich comprises normal and slightly branched hydrocarbons having aboiling range above about 40° C. and less than about 200° C., underaromatic conversion conditions with a catalyst comprising the molecularsieve of this invention made substantially free of acidity byneutralizing said molecular sieve with a basic metal. Also provided inthis invention is such a process wherein the molecular sieve contains aGroup VIII metal component.

Also provided by the present invention is a catalytic cracking processcomprising contacting a hydrocarbon feedstock in a reaction zone undercatalytic cracking conditions in the absence of added hydrogen with acatalyst comprising the molecular sieve of this invention, preferablypredominantly in the hydrogen form. Also included in this invention issuch a catalytic cracking process wherein the catalyst additionallycomprises a large pore crystalline cracking component.

This invention further provides an isomerization process for isomerizingC₄ to C₇ hydrocarbons, comprising contacting a feed having normal andslightly branched C₄ to C₇ hydrocarbons under isomerizing conditionswith a catalyst comprising the molecular sieve of this invention,preferably predominantly in the hydrogen form. The molecular sieve maybe impregnated with at least one Group VIII metal, preferably platinum.The catalyst may be calcined in a steam/air mixture at an elevatedtemperature after impregnation of the Group VIII metal.

Also provided by the present invention is a process for alkylating anaromatic hydrocarbon which comprises contacting under alkylationconditions at least a molar excess of an aromatic hydrocarbon with a C₂to C₂₀ olefin under at least partial liquid phase conditions and in thepresence of a catalyst comprising the molecular sieve of this invention,preferably predominantly in the hydrogen form. The olefin may be a C₂ toC₄ olefin, and the aromatic hydrocarbon and olefin may be present in amolar ratio of about 4:1 to about 20:1, respectively. The aromatichydrocarbon may be selected from the group consisting of benzene,toluene, ethylbenzene, xylene, naphthalene, naphthalene derivatives,dimethylnaphthalene or mixtures thereof.

Further provided in accordance with this invention is a process fortransalkylating an aromatic hydrocarbon which comprises contacting undertransalkylating conditions an aromatic hydrocarbon with a polyalkylaromatic hydrocarbon under at least partial liquid phase conditions andin the presence of a catalyst comprising the molecular sieve of thisinvention, preferably predominantly in the hydrogen form. The aromatichydrocarbon and the polyalkyl aromatic hydrocarbon may be present in amolar ratio of from about 1:1 to about 25:1, respectively.

The aromatic hydrocarbon may be selected from the group consisting ofbenzene, toluene, ethylbenzene, xylene, or mixtures thereof, and thepolyalkyl aromatic hydrocarbon may be a dialkylbenzene.

Further provided by this invention is a process to convert paraffins toaromatics which comprises contacting paraffins under conditions whichcause paraffins to convert to aromatics with a catalyst comprising themolecular sieve of this invention, said catalyst comprising gallium,zinc, or a compound of gallium or zinc.

In accordance with this invention there is also provided a process forisomerizing olefins comprising contacting said olefin under conditionswhich cause isomerization of the olefin with a catalyst comprising themolecular sieve of this invention.

Further provided in accordance with this invention is a process forisomerizing an isomerization feed comprising an aromatic C₈ stream ofxylene isomers or mixtures of xylene isomers and ethylbenzene, wherein amore nearly equilibrium ratio of ortho-, meta- and para-xylenes isobtained, said process comprising contacting said feed underisomerization conditions with a catalyst comprising the molecular sieveof this invention.

The present invention further provides a process for oligomerizingolefins comprising contacting an olefin feed under oligomerizationconditions with a catalyst comprising the molecular sieve of thisinvention.

This invention also provides a process for converting oxygenatedhydrocarbons comprising contacting said oxygenated hydrocarbon with acatalyst comprising the molecular sieve of this invention underconditions to produce liquid products. The oxygenated hydrocarbon may bea lower alcohol.

Further provided in accordance with the present invention is a processfor the production of higher molecular weight hydrocarbons from lowermolecular weight hydrocarbons comprising the steps of:

-   (a) introducing into a reaction zone a lower molecular weight    hydrocarbon-containing gas and contacting said gas in said zone    under C₂₊ hydrocarbon synthesis conditions with the catalyst and a    metal or metal compound capable of converting the lower molecular    weight hydrocarbon to a higher molecular weight hydrocarbon; and-   (b) withdrawing from said reaction zone a higher molecular weight    hydrocarbon-containing stream.

Also provided in accordance with this invention is a catalystcomposition for promoting polymerization of 1-olefins, said compositioncomprising

-   (A) a molecular sieve having a mole ratio greater than about 15    of (1) an oxide of a first tetravalent element to (2) an oxide of a    trivalent element, pentavalent element, second tetravalent element    which is different from said first tetravalent element or mixture    thereof and having, after calcination, the X-ray diffraction lines    of Table 2; and-   (B) an organotitanium or organochromium compound.

Oxide (1) may be silicon oxide, and oxide (2) may be an oxide selectedfrom aluminum oxide, gallium oxide, iron oxide, boron oxide, titaniumoxide, indium oxide.

The present invention further provides a for polymerizing 1-olefins,which process comprises contacting 1-olefin monomer with a catalyticallyeffective amount of a catalyst composition comprising

-   -   (A) a molecular sieve having a mole ratio greater than about 15        of (1) an oxide of a first tetravalent element to (2) an oxide        of a trivalent element, pentavalent element, second tetravalent        element which is different from said first tetravalent element        or mixture thereof and having, after calcination, the X-ray        diffraction lines of Table 2; and    -   (B) an organotitanium or organochromium compound        under polymerization conditions which include a temperature and        pressure suitable for initiating and promoting the        polymerization reaction.

Oxide (1) may be silicon oxide, and oxide (2) may be an oxide selectedfrom aluminum oxide, gallium oxide, iron oxide, boron oxide, titaniumoxide, indium oxide.

The present invention further provides a process for hydrogenating ahydrocarbon feed containing unsaturated hydrocarbons, the processcomprising contacting the feed and hydrogen under conditions which causehydrogenation with a catalyst comprising the molecular sieve of thisinvention. The catalyst can also contain metals, salts or complexeswherein the metal is selected from the group consisting of platinum,palladium, rhodium, iridium or combinations thereof, or the groupconsisting of nickel, molybdenum, cobalt, tungsten, titanium, chromium,vanadium, rhenium, manganese and combinations thereof.

In accordance with this invention, there is also provided a process forhydrotreating a hydrocarbon feedstock comprising contacting thefeedstock with a hydrotreating catalyst and hydrogen under hydrotreatingconditions, wherein the catalyst comprises the molecular sieve of thisinvention.

DETAILED DESCRIPTION OF THE INVENTION

The present invention comprises a family of crystalline molecular sievesdesignated herein “molecular sieve SSZ-56” or simply “SSZ-56”. Inpreparing SSZ-56, a N,N-diethyl-2-methyldecahydroquinolinium cation (thetrans-fused ring isomer) is used as a structure directing agent (“SDA”),also known as a crystallization template. The SDA useful for makingSSZ-56 has the following structure:

The SDA cation is associated with an anion (X⁻) which may be any anionthat is not detrimental to the formation of the molecular sieve.Representative anions include halogen, e.g., fluoride, chloride, bromideand iodide, hydroxide, acetate, sulfate, tetrafluoroborate, carboxylate,and the like. Hydroxide is the most preferred anion.

SSZ-56 is prepared from a reaction mixture having the composition shownin Table A below. TABLE A Reaction Mixture Typical PreferredYO₂/W_(a)O_(b) ≧15 30-60 OH—/YO₂ 0.10-0.50 0.20-0.30 Q/YO₂ 0.05-0.500.10-0.30 M_(2/n)/YO₂   0-0.40 0.10-0.25 H₂O/YO₂ 20-80 30-45where Y is silicon; W is aluminum, gallium, iron, boron, titanium,indium, vanadium or mixtures thereof; a is 1 or 2, b is 2 when a is 1(i.e., W is tetravalent); b is 3 when a is 2 (i.e., W is trivalent); Mis an alkali metal cation, alkaline earth metal cation or mixturesthereof; n is the valence of M (i.e., 1 or 2); and Q is a trans-fusedring N,N-diethyl-2-methyldecahydroquinolinium cation;

In practice, SSZ-56 is prepared by a process comprising:

-   -   (a) preparing an aqueous solution containing sources of oxides        capable of forming a crystalline molecular sieve and a        trans-fused ring N,N-diethyl-2-methyldecahydroquinolinium cation        having an anionic counterion which is not detrimental to the        formation of SSZ-56;    -   (b) maintaining the aqueous solution under conditions sufficient        to form crystals of SSZ-56; and    -   (c) recovering the crystals of SSZ-56.

Accordingly, SSZ-56 may comprise the crystalline material and the SDA incombination with metallic and non-metallic oxides bonded in tetrahedralcoordination through shared oxygen atoms to form a cross-linked threedimensional crystal structure.

Typical sources of silicon oxide include silicates, silica hydrogel,silicic acid, fumed silica, colloidal silica, tetra-alkylorthosilicates, and silica hydroxides. Boron can be added in formscorresponding to its silicon counterpart, such as boric acid.

A source zeolite reagent may provide a source of boron. In most cases,the source zeolite also provides a source of silica. The source zeolitein its deboronated form may also be used as a source of silica, withadditional silicon added using, for example, the conventional sourceslisted above. Use of a source zeolite reagent for the present process ismore completely described in U.S. Pat. No. 5,225,179, issued Jul. 6,1993 to Nakagawa entitled “Method of Making Molecular Sieves”, thedisclosure of which is incorporated herein by reference.

Typically, an alkali metal hydroxide and/or an alkaline earth metalhydroxide, such as the hydroxide of sodium, potassium, lithium, cesium,rubidium, calcium, and magnesium, is used in the reaction mixture;however, this component can be omitted so long as the equivalentbasicity is maintained. The SDA may be used to provide hydroxide ion.Thus, it may be beneficial to ion exchange, for example, the halide tohydroxide ion, thereby reducing or eliminating the alkali metalhydroxide quantity required. The alkali metal cation or alkaline earthcation may be part of the as-synthesized crystalline oxide material, inorder to balance valence electron charges therein.

The reaction mixture is maintained at an elevated temperature until thecrystals of the SSZ-56 are formed. The hydrothermal crystallization isusually conducted under autogenous pressure, at a temperature between100° C. and 200° C., preferably between 135° C. and 160° C. Thecrystallization period is typically greater than 1 day and preferablyfrom about 3 days to about 20 days.

Preferably, the molecular sieve is prepared using mild stirring oragitation.

During the hydrothermal crystallization step, the SSZ-56 crystals can beallowed to nucleate spontaneously from the reaction mixture. The use ofSSZ-56 crystals as seed material can be advantageous in decreasing thetime necessary for complete crystallization to occur. In addition,seeding can lead to an increased purity of the product obtained bypromoting the nucleation and/or formation of SSZ-56 over any undesiredphases. When used as seeds, SSZ-56 crystals are added in an amountbetween 0.1 and 10% of the weight of first tetravalent element oxide,e.g. silica, used in the reaction mixture.

Once the molecular sieve crystals have formed, the solid product isseparated from the reaction mixture by standard mechanical separationtechniques such as filtration. The crystals are water-washed and thendried, e.g., at 90° C. to 150° C. for from 8 to 24 hours, to obtain theas-synthesized SSZ-56 crystals. The drying step can be performed atatmospheric pressure or under vacuum.

SSZ-56 as prepared has a mole ratio of silicon oxide to boron oxidegreater than about 15; and has, after calcination, the X-ray diffractionlines of Table 2 below. SSZ-56 further has a composition, as synthesized(i.e., prior to removal of the SDA from the SSZ-56) and in the anhydrousstate, in terms of mole ratios, shown in Table B below. TABLE BAs-Synthesized SSZ-56 YO₂/W_(c)O_(d)   15-infinity M_(2/n)/YO₂   0-0.03Q/YO₂ 0.02-0.05where Y, W, M, n, and Q are as defined above and c is 1 or 2; d is 2when c is 1 (i.e., W is tetravalent) or d is 3 or 5 when c is 2 (i.e., dis 3 when W is trivalent or 5 when W is pentavalent).

SSZ-56 can be an all-silica. SSZ-56 is made as a borosilicate and thenthe boron can be removed, if desired, by treating the borosilicateSSZ-56 with acetic acid at elevated temperature (as described in Joneset al., Chem. Mater., 2001, 13, 1041-1050) to produce an all-silicaversion of SSZ-56 (i.e., YO₂/W_(c)O_(d) is ∞).

If desired, SSZ-56 can be made as a borosilicate and then the boron canbe removed as described above and replaced with metal atoms bytechniques known in the art. Aluminum, gallium, iron, titanium, vanadiumand mixtures thereof can be added in this manner.

It is believed that SSZ-56 is comprised of a new framework structure ortopology which is characterized by its X-ray diffraction pattern.SSZ-56, as-synthesized, has a crystalline structure whose X-ray powderdiffraction pattern exhibit the characteristic lines shown in Table 1and is thereby distinguished from other molecular sieves. TABLE 1 X-raydata for the as-synthesized Boron-SSZ-56 2θ^((a)) d RelativeIntensity^((b)) 6.58 13.43 M 7.43 11.88 M 7.93 11.14 S 8.41 10.51 M13.22 6.69 M 13.93 5.95 M 14.86 5.95 M 22.59 3.93 VS 23.26 3.82 VS 24.033.70 S^((a))±0.10^((b))The X-ray patterns provided are based on a relative intensityscale in which the strongest line in the X-ray pattern is assigned avalue of 100: W(weak) is less than 20; M(medium) is between 20 and 40;S(strong) is between 40 and 60; VS(very strong) is greater than 60.

Table 1A below shows the X-ray powder diffraction lines foras-synthesized SSZ-56 including actual relative intensities. TABLE 1AAs-Synthesized SSZ-56 I/Io × 100 2θ^((a)) d Relative Intensity 6.5813.42 36.3 7.43 11.88 25.2 7.93 11.14 58.5 8.41 10.51 30.9 8.84 10.0018.0 9.5 9.30 4.9 11.04 8.00 11.1 11.29 7.83 4.5 11.56 7.64 12.6 12.157.27 18.7 13.22 6.70 34.3 13.93 6.35 21.6 14.86 5.96 20.4 15.94 5.56 5.717.02 5.20 10.8 17.45 5.07 8.2 17.77 4.99 5.8 18.04 4.91 13.6 18.79 4.728.4 19.72 4.50 2.1 19.90 4.46 2.2 20.11 4.41 4.4 20.42 4.35 8.8 21.224.18 19.8 21.57 4.12 3.2 22.58 3.93 73.1 23.26 3.82 100.0 24.03 3.7048.9 25.04 3.55 5.7 25.32 3.51 4.1 25.49 3.49 3.5 25.99 3.42 12.9 26.583.35 10.2 26.86 3.32 7.2 28.33 3.15 6.6 28.86 3.09 13.3 29.41 3.03 3.529.68 3.00 5.1 30.07 2.97 9.4 31.07 2.88 2.2 32.08 2.79 5.9 32.82 2.732.7 34.13 2.62 4.9 34.97 2.56 3.4 37.49 2.39 2.9^((a))±0.10

After calcination, the SSZ-56 molecular sieves have a crystallinestructure whose X-ray powder diffraction pattern include thecharacteristic lines shown in Table 2: TABLE 2 X-ray data for calcinedSSZ-56 2θ d Relative Intensity 6.54 13.51 VS 7.36 11.97 VS 7.89 11.20 VS8.35 10.58 VS 8.81 10.03 S 13.16 6.72 M 14.83 5.96 M 22.48 3.95 VS 23.243.82 VS 23.99 3.70 S^((a))±0.10

Table 2A below shows the X-ray powder diffraction lines for calcinedSSZ-56 including actual relative intensities. TABLE 2A Calcined SSZ-56I/Io × 100 2θ^((a)) d Relative Intensity 6.54 13.51 70.0 7.38 11.97 69.37.89 11.20 85.2 8.35 10.58 68.7 8.81 10.03 43.2 11.23 7.87 14.7 11.527.68 5.6 12.09 7.31 9.9 13.16 6.72 23.3 13.89 6.37 11.1 14.42 6.14 9.314.83 5.97 38.5 15.89 5.57 8.1 16.95 5.22 6.0 17.41 5.09 5.4 17.75 5.006.7 17.96 4.93 6.3 18.75 4.73 7.7 19.05 4.66 3.3 20.00 4.44 7.5 20.364.36 5.0 21.15 4.19 16.9 21.55 4.12 4.5 22.48 3.95 63.0 23.24 3.82 100.023.99 3.71 44.8 25.15 3.54 4.4 25.41 3.50 2.6 25.96 3.43 15.6 26.51 3.3610.2 26.83 3.32 6.5 28.19 3.16 10.6 28.80 3.10 15.7 29.28 3.05 2.7 30.022.97 11.3 30.98 2.88 3.0 31.99 2.80 5.5 32.72 2.73 4.3 34.04 2.63 5.934.42 2.60 2.6 34.70 2.58 4.1 35.34 2.54 2.1 36.05 2.49 2.7 37.41 2.402.8 39.76 2.26 1.8^((a))±0.10

The X-ray powder diffraction patterns were determined by standardtechniques: The radiation was the K-alpha/doublet of copper. The peakheights and the positions, as a function of 2θ where θ is the Braggangle, were read from the relative intensities of the peaks, and d, theinterplanar spacing in Angstroms corresponding to the recorded lines,can be calculated.

The variation in the scattering angle (two theta) measurements, due toinstrument error and to differences between individual samples, isestimated at ±0.10 degrees.

The X-ray diffraction pattern of Table 1 is representative of“as-synthesized” or “as-made” SSZ-56 molecular sieves. Minor variationsin the diffraction pattern can result from variations in thesilica-to-boron mole ratio of the particular sample due to changes inlattice constants. In addition, sufficiently small crystals will affectthe shape and intensity of peaks, leading to significant peakbroadening.

Representative peaks from the X-ray diffraction pattern of calcinedSSZ-56 are shown in Table 2. Calcination can also result in changes inthe intensities of the peaks as compared to patterns of the “as-made”material, as well as minor shifts in the diffraction pattern. Themolecular sieve produced by exchanging the metal or other cationspresent in the molecular sieve with various other cations (such as H⁺ orNH₄ ⁺) yields essentially the same diffraction pattern, although again,there may be minor shifts in the interplanar spacing and variations inthe relative intensities of the peaks. Notwithstanding these minorperturbations, the basic crystal lattice remains unchanged by thesetreatments.

Crystalline SSZ-56 can be used as-synthesized, but preferably will bethermally treated (calcined). Usually, it is desirable to remove thealkali metal cation by ion exchange and replace it with hydrogen,ammonium, or any desired metal ion. The molecular sieve can be leachedwith chelating agents, e.g., EDTA or dilute acid solutions, to increasethe silica to alumina mole ratio. The molecular sieve can also besteamed; steaming helps stabilize the crystalline lattice to attack fromacids.

The molecular sieve can be used in intimate combination withhydrogenating components, such as tungsten, vanadium, molybdenum,rhenium, nickel, cobalt, chromium, manganese, or a noble metal, such aspalladium or platinum, for those applications in which ahydrogenation-dehydrogenation function is desired.

Metals may also be introduced into the molecular sieve by replacing someof the cations in the molecular sieve with metal cations via standardion exchange techniques (see, for example, U.S. Pat. No. 3,140,249issued Jul. 7, 1964 to Plank et al.; U.S. Pat. No. 3,140,251 issued Jul.7, 1964 to Plank et al.; and U.S. Pat. No. 3,140,253 issued Jul. 7, 1964to Plank et al.). Typical replacing cations can include metal cations,e.g., rare earth, Group IA, Group IIA and Group VIII metals, as well astheir mixtures. Of the replacing metallic cations, cations of metalssuch as rare earth, Mn, Ca, Mg, Zn, Cd, Pt, Pd, Ni, Co, Ti, Al, Sn, andFe are particularly preferred.

The hydrogen, ammonium, and metal components can be ion-exchanged intothe SSZ-56. The SSZ-56 can also be impregnated with the metals, or themetals can be physically and intimately admixed with the SSZ-56 usingstandard methods known to the art.

Typical ion-exchange techniques involve contacting the syntheticmolecular sieve with a solution containing a salt of the desiredreplacing cation or cations. Although a wide variety of salts can beemployed, chlorides and other halides, acetates, nitrates, and sulfatesare particularly preferred. The molecular sieve is usually calcinedprior to the ion-exchange procedure to remove the organic matter presentin the channels and on the surface, since this results in a moreeffective ion exchange. Representative ion exchange techniques aredisclosed in a wide variety of patents including U.S. Pat. No. 3,140,249issued on Jul. 7, 1964 to Plank et al.; U.S. Pat. No. 3,140,251 issuedon Jul. 7, 1964 to Plank et al.; and U.S. Pat. No. 3,140,253 issued onJul. 7, 1964 to Plank et al.

Following contact with the salt solution of the desired replacingcation, the molecular sieve is typically washed with water and dried attemperatures ranging from 65° C. to about 200° C. After washing, themolecular sieve can be calcined in air or inert gas at temperaturesranging from about 200° C. to about 800° C. for periods of time rangingfrom 1 to 48 hours, or more, to produce a catalytically active productespecially useful in hydrocarbon conversion processes.

Regardless of the cations present in the synthesized form of SSZ-56, thespatial arrangement of the atoms which form the basic crystal lattice ofthe molecular sieve remains essentially unchanged.

SSZ-56 can be formed into a wide variety of physical shapes. Generallyspeaking, the molecular sieve can be in the form of a powder, a granule,or a molded product, such as extrudate having a particle size sufficientto pass through a 2-mesh (Tyler) screen and be retained on a 400-mesh(Tyler) screen. In cases where the catalyst is molded, such as byextrusion with an organic binder, the SSZ-56 can be extruded beforedrying, or, dried or partially dried and then extruded.

SSZ-56 can be composited with other materials resistant to thetemperatures and other conditions employed in organic conversionprocesses. Such matrix materials include active and inactive materialsand synthetic or naturally occurring zeolites as well as inorganicmaterials such as clays, silica and metal oxides. Examples of suchmaterials and the manner in which they can be used are disclosed in U.S.Pat. No. 4,910,006, issued May 20, 1990 to Zones et al., and U.S. Pat.No. 5,316,753, issued May 31, 1994 to Nakagawa, both of which areincorporated by reference herein in their entirety.

Hydrocarbon Conversion Processes

SSZ-56 zeolites are useful in hydrocarbon conversion reactions.Hydrocarbon conversion reactions are chemical and catalytic processes inwhich carbon containing compounds are changed to different carboncontaining compounds. Examples of hydrocarbon conversion reactions inwhich SSZ-56 are expected to be useful include hydrocracking, dewaxing,catalytic cracking and olefin and aromatics formation reactions. Thecatalysts are also expected to be useful in other petroleum refining andhydrocarbon conversion reactions such as isomerizing n-paraffins andnaphthenes, polymerizing and oligomerizing olefinic or acetyleniccompounds such as isobutylene and butene-1, polymerization of 1-olefins(e.g., ethylene), reforming, isomerizing polyalkyl substituted aromatics(e.g., m-xylene), and disproportionating aromatics (e.g., toluene) toprovide mixtures of benzene, xylenes and higher methylbenzenes andoxidation reactions. Also included are rearrangement reactions to makevarious naphthalene derivatives, and forming higher molecular weighthydrocarbons from lower molecular weight hydrocarbons (e.g., methaneupgrading).

The SSZ-56 catalysts may have high selectivity, and under hydrocarbonconversion conditions can provide a high percentage of desired productsrelative to total products.

For high catalytic activity, the SSZ-56 zeolite should be predominantlyin its hydrogen ion form. Generally, the zeolite is converted to itshydrogen form by ammonium exchange followed by calcination. If thezeolite is synthesized with a high enough ratio of SDA cation to sodiumion, calcination alone may be sufficient. It is preferred that, aftercalcination, at least 80% of the cation sites are occupied by hydrogenions and/or rare earth ions. As used herein, “predominantly in thehydrogen form” means that, after calcination, at least 80% of the cationsites are occupied by hydrogen ions and/or rare earth ions.

SSZ-56 zeolites can be used in processing hydrocarbonaceous feedstocks.Hydrocarbonaceous feedstocks contain carbon compounds and can be frommany different sources, such as virgin petroleum fractions, recyclepetroleum fractions, shale oil, liquefied coal, tar sand oil, syntheticparaffins from NAO, recycled plastic feedstocks and, in general, can beany carbon containing feedstock susceptible to zeolitic catalyticreactions. Depending on the type of processing the hydrocarbonaceousfeed is to undergo, the feed can contain metal or be free of metals, itcan also have high or low nitrogen or sulfur impurities. It can beappreciated, however, that in general processing will be more efficient(and the catalyst more active) the lower the metal, nitrogen, and sulfurcontent of the feedstock.

The conversion of hydrocarbonaceous feeds can take place in anyconvenient mode, for example, in fluidized bed, moving bed, or fixed bedreactors depending on the types of process desired. The formulation ofthe catalyst particles will vary depending on the conversion process andmethod of operation.

Other reactions which can be performed using the catalyst of thisinvention containing a metal, e.g., a Group VIII metal such platinum,include hydrogenation-dehydrogenation reactions, denitrogenation anddesulfurization reactions.

The following table indicates typical reaction conditions which may beemployed when using catalysts comprising SSZ-56 in the hydrocarbonconversion reactions of this invention. Preferred conditions areindicated in parentheses. Process Temp., ° C. Pressure LHSVHydrocracking 175-485 0.5-350 bar 0.1-30  Dewaxing 200-475 15-3000 psig,0.1-20  (250-450) 0.103-20.7 Mpa (0.2-10)  gauge (200-3000, 1.38-20.7Mpa gauge) Aromatics 400-600 atm.-10 bar 0.1-15  formation (480-550)Cat. Cracking 127-885 subatm.-¹ 0.5-50  (atm.-5 atm.) Oligomerization232-649² 0.1-50 atm^(2,3) 0.2-50²   10-232⁴ — 0.05-20⁵    (27-204)⁴ —(0.1-10)⁵ Paraffins to 100-700 0-1000 psig 0.5-40⁵ aromaticsCondensation of 260-538 0.5-1000 psig, 0.5-50⁵ alcohols 0.00345-6.89 Mpagauge Isomerization  93-538 50-1000 psig,  1-10 (204-315) 0.345-6.89 Mpa(1-4) gauge Xylene  260-593² 0.5-50 atm.²  0.1-100⁵ isomerization (315-566)² (1-5 atm)² (0.5-50)⁵   38-371⁴ 1-200 atm.⁴ 0.5-50 ¹Several hundred atmospheres²Gas phase reaction³Hydrocarbon partial pressure⁴Liquid phase reaction⁵WHSVOther reaction conditions and parameters are provided below.

Hydrocracking

Using a catalyst which comprises SSZ-56, preferably predominantly in thehydrogen form, and a hydrogenation promoter, heavy petroleum residualfeedstocks, cyclic stocks and other hydrocrackate charge stocks can behydrocracked using the process conditions and catalyst componentsdisclosed in the aforementioned U.S. Pat. No. 4,910,006 and U.S. Pat.No. 5,316,753.

The hydrocracking catalysts contain an effective amount of at least onehydrogenation component of the type commonly employed in hydrocrackingcatalysts. The hydrogenation component is generally selected from thegroup of hydrogenation catalysts consisting of one or more metals ofGroup VIB and Group VIII, including the salts, complexes and solutionscontaining such. The hydrogenation catalyst is preferably selected fromthe group of metals, salts and complexes thereof of the group consistingof at least one of platinum, palladium, rhodium, iridium, ruthenium andmixtures thereof or the group consisting of at least one of nickel,molybdenum, cobalt, tungsten, titanium, chromium and mixtures thereof.Reference to the catalytically active metal or metals is intended toencompass such metal or metals in the elemental state or in some formsuch as an oxide, sulfide, halide, carboxylate and the like. Thehydrogenation catalyst is present in an effective amount to provide thehydrogenation function of the hydrocracking catalyst, and preferably inthe range of from 0.05 to 25% by weight.

Dewaxing

SSZ-56, preferably predominantly in the hydrogen form, can be used todewax hydrocarbonaceous feeds by selectively removing straight chainparaffins. Typically, the viscosity index of the dewaxed product isimproved (compared to the waxy feed) when the waxy feed is contactedwith SSZ-56 under isomerization dewaxing conditions.

The catalytic dewaxing conditions are dependent in large measure on thefeed used and upon the desired pour point. Hydrogen is preferablypresent in the reaction zone during the catalytic dewaxing process. Thehydrogen to feed ratio is typically between about 500 and about 30,000SCF/bbl (standard cubic feet per barrel) (0.089 to 5.34 SCM/liter(standard cubic meters/liter)), preferably about 1000 to about 20,000SCF/bbl (0.178 to 3.56 SCM/liter). Generally, hydrogen will be separatedfrom the product and recycled to the reaction zone. Typical feedstocksinclude light gas oil, heavy gas oils and reduced crudes boiling aboveabout 350° F. (177° C.).

A typical dewaxing process is the catalytic dewaxing of a hydrocarbonoil feedstock boiling above about 350° F. (177° C.) and containingstraight chain and slightly branched chain hydrocarbons by contactingthe hydrocarbon oil feedstock in the presence of added hydrogen gas at ahydrogen pressure of about 15-3000 psi (0.103-20.7 Mpa) with a catalystcomprising SSZ-56 and at least one Group VIII metal.

The SSZ-56 hydrodewaxing catalyst may optionally contain a hydrogenationcomponent of the type commonly employed in dewaxing catalysts. See theaforementioned U.S. Pat. No. 4,910,006 and U.S. Pat. No. 5,316,753 forexamples of these hydrogenation components.

The hydrogenation component is present in an effective amount to providean effective hydrodewaxing and hydroisomerization catalyst preferably inthe range of from about 0.05 to 5% by weight. The catalyst may be run insuch a mode to increase isomerization dewaxing at the expense ofcracking reactions.

The feed may be hydrocracked, followed by dewaxing. This type of twostage process and typical hydrocracking conditions are described in U.S.Pat. No. 4,921,594, issued May 1, 1990 to Miller, which is incorporatedherein by reference in its entirety.

SSZ-56 may also be utilized as a dewaxing catalyst in the form of alayered catalyst. That is, the catalyst comprises a first layercomprising zeolite SSZ-56 and at least one Group VIII metal, and asecond layer comprising an aluminosilicate zeolite which is more shapeselective than zeolite SSZ-56. The use of layered catalysts is disclosedin U.S. Pat. No. 5,149,421, issued Sep. 22, 1992 to Miller, which isincorporated by reference herein in its entirety. The layering may alsoinclude a bed of SSZ-56 layered with a non-zeolitic component designedfor either hydrocracking or hydrofinishing.

SSZ-56 may also be used to dewax raffinates, including bright stock,under conditions such as those disclosed in U.S. Pat. No. 4,181,598,issued Jan. 1, 1980 to Gillespie et al., which is incorporated byreference herein in its entirety.

It is often desirable to use mild hydrogenation (sometimes referred toas hydrofinishing) to produce more stable dewaxed products. Thehydrofinishing step can be performed either before or after the dewaxingstep, and preferably after. Hydrofinishing is typically conducted attemperatures ranging from about 190° C. to about 340° C. at pressuresfrom about 400 psig to about 3000 psig (2.76 to 20.7 Mpa gauge) at spacevelocities (LHSV) between about 0.1 and 20 and a hydrogen recycle rateof about 400 to 1500 SCF/bbl (0.071 to 0.27 SCM/liter). Thehydrogenation catalyst employed must be active enough not only tohydrogenate the olefins, diolefins and color bodies which may bepresent, but also to reduce the aromatic content. Suitable hydrogenationcatalyst are disclosed in U.S. Pat. No. 4,921,594, issued May 1, 1990 toMiller, which is incorporated by reference herein in its entirety. Thehydrofinishing step is beneficial in preparing an acceptably stableproduct (e.g., a lubricating oil) since dewaxed products prepared fromhydrocracked stocks tend to be unstable to air and light and tend toform sludges spontaneously and quickly.

Lube oil may be prepared using SSZ-56. For example, a C₂₀₊ lube oil maybe made by isomerizing a C₂₀₊ olefin feed over a catalyst comprisingSSZ-56 in the hydrogen form and at least one Group VIII metal.Alternatively, the lubricating oil may be made by hydrocracking in ahydrocracking zone a hydrocarbonaceous feedstock to obtain an effluentcomprising a hydrocracked oil, and catalytically dewaxing the effluentat a temperature of at least about 400° F. (204° C.) and at a pressureof from about 15 psig to about 3000 psig (0.103-20.7 Mpa gauge) in thepresence of added hydrogen gas with a catalyst comprising SSZ-56 in thehydrogen form and at least one Group VIII metal.

Aromatics Formation

SSZ-56 can be used to convert light straight run naphthas and similarmixtures to highly aromatic mixtures. Thus, normal and slightly branchedchained hydrocarbons, preferably having a boiling range above about 40°C. and less than about 200° C., can be converted to products having asubstantial higher octane aromatics content by contacting thehydrocarbon feed with a catalyst comprising SSZ-56. It is also possibleto convert heavier feeds into BTX or naphthalene derivatives of valueusing a catalyst comprising SSZ-56.

The conversion catalyst preferably contains a Group VIII metal compoundto have sufficient activity for commercial use. By Group VIII metalcompound as used herein is meant the metal itself or a compound thereof.The Group VIII noble metals and their compounds, platinum, palladium,and iridium, or combinations thereof can be used. Rhenium or tin or amixture thereof may also be used in conjunction with the Group VIIImetal compound and preferably a noble metal compound. The most preferredmetal is platinum. The amount of Group VIII metal present in theconversion catalyst should be within the normal range of use inreforming catalysts, from about 0.05 to 2.0 weight percent, preferably0.2 to 0.8 weight percent.

It is critical to the selective production of aromatics in usefulquantities that the conversion catalyst be substantially free ofacidity, for example, by neutralizing the zeolite with a basic metal,e.g., alkali metal, compound. Methods for rendering the catalyst free ofacidity are known in the art. See the aforementioned U.S. Pat. No.4,910,006 and U.S. Pat. No. 5,316,753 for a description of such methods.

The preferred alkali metals are sodium, potassium, rubidium and cesium.The zeolite itself can be substantially free of acidity only at veryhigh silica:alumina mole ratios.

Catalytic Cracking

Hydrocarbon cracking stocks can be catalytically cracked in the absenceof hydrogen using SSZ-56, preferably predominantly in the hydrogen form.

When SSZ-56 is used as a catalytic cracking catalyst in the absence ofhydrogen, the catalyst may be employed in conjunction with traditionalcracking catalysts, e.g., any aluminosilicate heretofore employed as acomponent in cracking catalysts. Typically, these are large pore,crystalline aluminosilicates. Examples of these traditional crackingcatalysts are disclosed in the aforementioned U.S. Pat. No. 4,910,006and U.S. Pat. No. 5,316,753. When a traditional cracking catalyst (TC)component is employed, the relative weight ratio of the TC to the SSZ-56is generally between about 1:10 and about 500:1, desirably between about1:10 and about 200:1, preferably between about 1:2 and about 50:1, andmost preferably is between about 1:1 and about 20:1. The novel zeoliteand/or the traditional cracking component may be further ion exchangedwith rare earth ions to modify selectivity.

The cracking catalysts are typically employed with an inorganic oxidematrix component. See the aforementioned U.S. Pat. No. 4,910,006 andU.S. Pat. No. 5,316,753 for examples of such matrix components.

Isomerization

The present catalyst is highly active and highly selective forisomerizing C₄ to C₇ hydrocarbons. The activity means that the catalystcan operate at relatively low temperature which thermodynamically favorshighly branched paraffins. Consequently, the catalyst can produce a highoctane product. The high selectivity means that a relatively high liquidyield can be achieved when the catalyst is run at a high octane.

The present process comprises contacting the isomerization catalyst,i.e., a catalyst comprising SSZ-56 in the hydrogen form, with ahydrocarbon feed under isomerization conditions. The feed is preferablya light straight run fraction, boiling within the range of 30° F. to250° F. (−1° C. to 121° C.) and preferably from 60° F. to 200° F. (16°C. to 93° C.). Preferably, the hydrocarbon feed for the processcomprises a substantial amount of C₄ to C₇ normal and slightly branchedlow octane hydrocarbons, more preferably C₅ and C₆ hydrocarbons.

It is preferable to carry out the isomerization reaction in the presenceof hydrogen. Preferably, hydrogen is added to give a hydrogen tohydrocarbon ratio (H₂/HC) of between 0.5 and 10 H₂/HC, more preferablybetween 1 and 8 H₂/HC. See the aforementioned U.S. Pat. No. 4,910,006and U.S. Pat. No. 5,316,753 for a further discussion of isomerizationprocess conditions.

A low sulfur feed is especially preferred in the present process. Thefeed preferably contains less than 10 ppm, more preferably less than 1ppm, and most preferably less than 0.1 ppm sulfur. In the case of a feedwhich is not already low in sulfur, acceptable levels can be reached byhydrogenating the feed in a presaturation zone with a hydrogenatingcatalyst which is resistant to sulfur poisoning. See the aforementionedU.S. Pat. No. 4,910,006 and U.S. Pat. No. 5,316,753 for a furtherdiscussion of this hydrodesulfurization process.

It is preferable to limit the nitrogen level and the water content ofthe feed. Catalysts and processes which are suitable for these purposesare known to those skilled in the art.

After a period of operation, the catalyst can become deactivated bysulfur or coke. See the aforementioned U.S. Pat. No. 4,910,006 and U.S.Pat. No. 5,316,753 for a further discussion of methods of removing thissulfur and coke, and of regenerating the catalyst.

The conversion catalyst preferably contains a Group VIII metal compoundto have sufficient activity for commercial use. By Group VIII metalcompound as used herein is meant the metal itself or a compound thereof.The Group VIII noble metals and their compounds, platinum, palladium,and iridium, or combinations thereof can be used. Rhenium and tin mayalso be used in conjunction with the noble metal. The most preferredmetal is platinum. The amount of Group VIII metal present in theconversion catalyst should be within the normal range of use inisomerizing catalysts, from about 0.05 to 2.0 weight percent, preferably0.2 to 0.8 weight percent.

Alkylation and Transalkylation

SSZ-56 can be used in a process for the alkylation or transalkylation ofan aromatic hydrocarbon. The process comprises contacting the aromatichydrocarbon with a C₂ to C₁₆ olefin alkylating agent or a polyalkylaromatic hydrocarbon transalkylating agent, under at least partialliquid phase conditions, and in the presence of a catalyst comprisingSSZ-56.

SSZ-56 can also be used for removing benzene from gasoline by alkylatingthe benzene as described above and removing the alkylated product fromthe gasoline.

For high catalytic activity, the SSZ-56 zeolite should be predominantlyin its hydrogen ion form. It is preferred that, after calcination, atleast 80% of the cation sites are occupied by hydrogen ions and/or rareearth ions.

Examples of suitable aromatic hydrocarbon feedstocks which may bealkylated or transalkylated by the process of the invention includearomatic compounds such as benzene, toluene and xylene. The preferredaromatic hydrocarbon is benzene. There may be occasions wherenaphthalene or naphthalene derivatives such as dimethylnaphthalene maybe desirable. Mixtures of aromatic hydrocarbons may also be employed.

Suitable olefins for the alkylation of the aromatic hydrocarbon arethose containing 2 to 20, preferably 2 to 4, carbon atoms, such asethylene, propylene, butene-1, trans-butene-2 and cis-butene-2, ormixtures thereof. There may be instances where pentenes are desirable.The preferred olefins are ethylene and propylene. Longer chain alphaolefins may be used as well.

When transalkylation is desired, the transalkylating agent is apolyalkyl aromatic hydrocarbon containing two or more alkyl groups thateach may have from 2 to about 4 carbon atoms. For example, suitablepolyalkyl aromatic hydrocarbons include di-, tri- and tetra-alkylaromatic hydrocarbons, such as diethylbenzene, triethylbenzene,diethylmethylbenzene (diethyltoluene), di-isopropylbenzene,di-isopropyltoluene, dibutylbenzene, and the like. Preferred polyalkylaromatic hydrocarbons are the dialkyl benzenes. A particularly preferredpolyalkyl aromatic hydrocarbon is di-isopropylbenzene.

When alkylation is the process conducted, reaction conditions are asfollows. The aromatic hydrocarbon feed should be present instoichiometric excess. It is preferred that molar ratio of aromatics toolefins be greater than four-to-one to prevent rapid catalyst fouling.The reaction temperature may range from 100° F. to 600° F. (38° C. to315° C.), preferably 250° F. to 450° F. (121° C. to 232° C.). Thereaction pressure should be sufficient to maintain at least a partialliquid phase in order to retard catalyst fouling. This is typically 50psig to 1000 psig (0.345 to 6.89 Mpa gauge) depending on the feedstockand reaction temperature. Contact time may range from 10 seconds to 10hours, but is usually from 5 minutes to an hour. The weight hourly spacevelocity (WHSV), in terms of grams (pounds) of aromatic hydrocarbon andolefin per gram (pound) of catalyst per hour, is generally within therange of about 0.5 to 50.

When transalkylation is the process conducted, the molar ratio ofaromatic hydrocarbon will generally range from about 1:1 to 25:1, andpreferably from about 2:1 to 20:1. The reaction temperature may rangefrom about 100° F. to 600° F. (38° C. to 315° C.), but it is preferablyabout 250° F. to 450° F. (121° C. to 232° C.). The reaction pressureshould be sufficient to maintain at least a partial liquid phase,typically in the range of about 50 psig to 1000 psig (0.345 to 6.89 Mpagauge), preferably 300 psig to 600 psig (2.07 to 4.14 Mpa gauge). Theweight hourly space velocity will range from about 0.1 to 10. U.S. Pat.No. 5,082,990 issued on Jan. 21, 1992 to Hsieh, et al. describes suchprocesses and is incorporated herein by reference.

Conversion of Paraffins to Aromatics

SSZ-56 can be used to convert light gas C₂-C₆ paraffins to highermolecular weight hydrocarbons including aromatic compounds. Preferably,the zeolite will contain a catalyst metal or metal oxide wherein saidmetal is selected from the group consisting of Groups IB, IIB, VIII andIIIA of the Periodic Table. Preferably, the metal is gallium, niobium,indium or zinc in the range of from about 0.05 to 5% by weight.

Isomerization of Olefins

SSZ-56 can be used to isomerize olefins. The feed stream is ahydrocarbon stream containing at least one C₄₋₆ olefin, preferably aC₄₋₆ normal olefin, more preferably normal butene. Normal butene as usedin this specification means all forms of normal butene, e.g., 1-butene,cis-2-butene, and trans-2-butene. Typically, hydrocarbons other thannormal butene or other C₄₋₆ normal olefins will be present in the feedstream. These other hydrocarbons may include, e.g., alkanes, otherolefins, aromatics, hydrogen, and inert gases.

The feed stream typically may be the effluent from a fluid catalyticcracking unit or a methyl-tert-butyl ether unit. A fluid catalyticcracking unit effluent typically contains about 40-60 weight percentnormal butenes. A methyl-tert-butyl ether unit effluent typicallycontains 40-100 weight percent normal butene. The feed stream preferablycontains at least about 40 weight percent normal butene, more preferablyat least about 65 weight percent normal butene. The terms iso-olefin andmethyl branched iso-olefin may be used interchangeably in thisspecification.

The process is carried out under isomerization conditions. Thehydrocarbon feed is contacted in a vapor phase with a catalystcomprising the SSZ-56. The process may be carried out generally at atemperature from about 625° F. to about 950° F. (329-510° C.), forbutenes, preferably from about 700° F. to about 900° F. (371-482° C.),and about 350° F. to about 650° F. (177-343° C.) for pentenes andhexenes. The pressure ranges from subatmospheric to about 200 psig (1.38Mpa gauge), preferably from about 15 psig to about 200 psig (0.103 to1.38 Mpa gauge), and more preferably from about 1 psig to about 150 psig(0.00689 to 1.03 Mpa gauge).

The liquid hourly space velocity during contacting is generally fromabout 0.1 to about 50 hr⁻¹, based on the hydrocarbon feed, preferablyfrom about 0.1 to about 20 hr⁻¹, more preferably from about 0.2 to about10 hr⁻¹, most preferably from about 1 to about 5 hr⁻¹. Ahydrogen/hydrocarbon molar ratio is maintained from about 0 to about 30or higher. The hydrogen can be added directly to the feed stream ordirectly to the isomerization zone. The reaction is preferablysubstantially free of water, typically less than about two weightpercent based on the feed. The process can be carried out in a packedbed reactor, a fixed bed, fluidized bed reactor, or a moving bedreactor. The bed of the catalyst can move upward or downward. The molepercent conversion of, e.g., normal butene to iso-butene is at least 10,preferably at least 25, and more preferably at least 35.

Xylene Isomerization

SSZ-56 may also be useful in a process for isomerizing one or morexylene isomers in a C₈ aromatic feed to obtain ortho-, meta-, andpara-xylene in a ratio approaching the equilibrium value. In particular,xylene isomerization is used in conjunction with a separate process tomanufacture para-xylene. For example, a portion of the para-xylene in amixed C₈ aromatics stream may be recovered by crystallization andcentrifugation. The mother liquor from the crystallizer is then reactedunder xylene isomerization conditions to restore ortho-, meta- andpara-xylenes to a near equilibrium ratio. At the same time, part of theethylbenzene in the mother liquor is converted to xylenes or to productswhich are easily separated by filtration. The isomerate is blended withfresh feed and the combined stream is distilled to remove heavy andlight by-products. The resultant C₈ aromatics stream is then sent to thecrystallizer to repeat the cycle.

Optionally, isomerization in the vapor phase is conducted in thepresence of 3.0 to 30.0 moles of hydrogen per mole of alkylbenzene(e.g., ethylbenzene). If hydrogen is used, the catalyst should compriseabout 0.1 to 2.0 wt. % of a hydrogenation/dehydrogenation componentselected from Group VIII (of the Periodic Table) metal component,especially platinum or nickel. By Group VIII metal component is meantthe metals and their compounds such as oxides and sulfides.

Optionally, the isomerization feed may contain 10 to 90 wt. of a diluentsuch as toluene, trimethylbenzene, naphthenes or paraffins.

Oligomerization

It is expected that SSZ-56 can also be used to oligomerize straight andbranched chain olefins having from about 2 to 21 and preferably 2-5carbon atoms. The oligomers which are the products of the process aremedium to heavy olefins which are useful for both fuels, i.e., gasolineor a gasoline blending stock and chemicals.

The oligomerization process comprises contacting the olefin feedstock inthe gaseous or liquid phase with a catalyst comprising SSZ-56.

The zeolite can have the original cations associated therewith replacedby a wide variety of other cations according to techniques well known inthe art. Typical cations would include hydrogen, ammonium and metalcations including mixtures of the same. Of the replacing metalliccations, particular preference is given to cations of metals such asrare earth metals, manganese, calcium, as well as metals of Group II ofthe Periodic Table, e.g., zinc, and Group VIII of the Periodic Table,e.g., nickel. One of the prime requisites is that the zeolite have afairly low aromatization activity, i.e., in which the amount ofaromatics produced is not more than about 20% by weight. This isaccomplished by using a zeolite with controlled acid activity [alphavalue] of from about 0.1 to about 120, preferably from about 0.1 toabout 100, as measured by its ability to crack n-hexane.

Alpha values are defined by a standard test known in the art, e.g., asshown in U.S. Pat. No. 3,960,978 issued on Jun. 1, 1976 to Givens et al.which is incorporated totally herein by reference. If required, suchzeolites may be obtained by steaming, by use in a conversion process orby any other method which may occur to one skilled in this art.

Condensation of Alcohols

SSZ-56 can be used to condense lower aliphatic alcohols having 1 to 10carbon atoms to a gasoline boiling point hydrocarbon product comprisingmixed aliphatic and aromatic hydrocarbon. The process disclosed in U.S.Pat. No. 3,894,107, issued Jul. 8, 1975 to Butter et al., describes theprocess conditions used in this process, which patent is incorporatedtotally herein by reference.

The catalyst may be in the hydrogen form or may be base exchanged orimpregnated to contain ammonium or a metal cation complement, preferablyin the range of from about 0.05 to 5% by weight. The metal cations thatmay be present include any of the metals of the Groups I through VIII ofthe Periodic Table. However, in the case of Group IA metals, the cationcontent should in no case be so large as to effectively inactivate thecatalyst, nor should the exchange be such as to eliminate all acidity.There may be other processes involving treatment of oxygenatedsubstrates where a basic catalyst is desired.

Methane Upgrading

Higher molecular weight hydrocarbons can be formed from lower molecularweight hydrocarbons by contacting the lower molecular weight hydrocarbonwith a catalyst comprising SSZ-56 and a metal or metal compound capableof converting the lower molecular weight hydrocarbon to a highermolecular weight hydrocarbon. Examples of such reactions include theconversion of methane to C₂₊ hydrocarbons such as ethylene or benzene orboth. Examples of useful metals and metal compounds include lanthanideand or actinide metals or metal compounds.

These reactions, the metals or metal compounds employed and theconditions under which they can be run are disclosed in U.S. Pat. No.4,734,537, issued Mar. 29, 1988 to Devries et al.; U.S. Pat. No.4,939,311, issued Jul. 3, 1990 to Washecheck et al.; U.S. Pat. No.4,962,261, issued Oct. 9,1990 to Abrevaya et al.; U.S. Pat. No.5,095,161, issued Mar. 10, 1992 to Abrevaya et al.; U.S. Pat. No.5,105,044, issued Apr. 14, 1992 to Han et al.; U.S. Pat. No. 5,105,046,issued Apr. 14, 1992 to Washecheck; U.S. Pat. No. 5,238,898, issued Aug.24, 1993 to Han et al.; U.S. Pat. No. 5,321,185, issued Jun. 14, 1994 tovan der Vaart; and U.S. Pat. No. 5,336,825, issued Aug. 9, 1994 toChoudhary et al., each of which is incorporated herein by reference inits entirety.

Polymerization of 1-Olefins

The molecular sieve of the present invention may be used in a catalystfor the polymerization of 1-olefins, e.g., the polymerization ofethylene. To form the olefin polymerization catalyst, the molecularsieve as hereinbefore described is reacted with a particular type oforganometallic compound. Organometallic compounds useful in forming thepolymerization catalyst include trivalent and tetravalent organotitaniumand organochromium compounds having alkyl moieties and, optionally, halomoieties. In the context of the present invention the term “alkyl”includes both straight and branched chain alkyl, cycloalkyl and alkarylgroups such as benzyl.

Examples of trivalent and tetravalent organochromium and organotitaniumcompounds are disclosed in U.S. Pat. No. 4,376,722, issued Mar. 15, 1983to Chester et al., U.S. Pat. No. 4,377,497, issued Mar. 22, 1983 toChester et al., U.S. Pat. No. 4,446,243, issued May 1, 1984 to Chesteret al., and U.S. Pat. No. 4,526,942, issued Jul. 2, 1985 to Chester etal. The disclosure of the aforementioned patents are incorporated hereinby reference in their entirety.

Examples of the organometallic compounds used to form the polymerizationcatalyst include, but are not limited to, compounds corresponding to thegeneral formula:MY_(n)X_(m-n)wherein M is a metal selected from titanium and chromium; Y is alkyl; Xis halogen (e.g., Cl or Br); n is 1-4; and m is greater than or equal ton and is 3 or 4.

Examples of organotitanium and organochromium compounds encompassed bysuch a formula include compounds of the formula CrY₄, CrY₃, CrY₃X,CrY₂X, CrY₂X₂, CrYX₂, CrYX₃, TiY₄, TiY₃, TiY₃X, TiY₂X, TiY₂Y₂, TiYX₂,TiYX₃, wherein X can be Cl or Br and Y can be methyl, ethyl, propyl,isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl,neopentyl, hexyl, isohexyl, neohexyl, 2-ethybutyl, octyl, 2-ethylhexyl,2,2-diethylbutyl, 2-isopropyl-3-methylbutyl, etc., cyclohexylalkyls suchas, for example, cyclohexylmethyl, 2-cyclohexylethyl,3-cyclyhexylpropyl, 4-cyclohexylbutyl, and the correspondingalkyl-substituted cyclohexyl radicals as, for example,(4-methylcyclohexyl)methyl, neophyl, i.e., beta,beta-dimethyl-phenethyl, benzyl, ethylbenzyl, and p-isopropylbenzyl.Preferred examples of Y include C₁₋₅ alkyl, especially butyl.

The organotitanium and organochromium materials employed in the catalystcan be prepared by techniques well known in the art. See, for examplethe aforementioned Chester et al. patents.

The organotitanium or organochromium compounds can be with the molecularsieve of the present invention, such as by reacting the organometalliccompound and the molecular sieve, in order to form the olefinpolymerization catalyst. Generally, such a reaction takes place in thesame reaction medium used to prepare the organometallic compound underconditions which promote formation of such a reaction product. Themolecular sieve can simply be added to the reaction mixture afterformation of the organometallic compound has been completed. Molecularsieve is added in an amount sufficient to provide from about 0.1 to 10parts by weight, preferably from about 0.5 to 5 parts by weight, oforganometallic compound in the reaction medium per 100 parts by weightof molecular sieve.

Temperature of the reaction medium during reaction of organometalliccompound with molecular sieve is also maintained at a level which is lowenough to ensure the stability of the organometallic reactant. Thus,temperatures in the range of from about −150° C. to 50° C., preferablyfrom about −80° C. to 0° C. can be usefully employed. Reaction times offrom about 0.01 to 10 hours, more preferably from about 0.1 to 1 hour,can be employed in reacting the organotitanium or organochromiumcompound with the molecular sieve.

Upon completion of the reaction, the catalyst material so formed may berecovered and dried by evaporating the reaction medium solvent under anitrogen atmosphere. Alternatively, olefin polymerization reactions canbe conducted in this same solvent based reaction medium used to form thecatalyst.

The polymerization catalyst can be used to catalyze polymerization of1-olefins. The polymers produced using the catalysts of this inventionare normally solid polymers of at least one mono-1-olefin containingfrom 2 to 8 carbon atoms per molecule. These polymers are normally solidhomopolymers of ethylene or copolymers of ethylene with anothermono-1-olefin containing 3 to 8 carbon atoms per molecule. Exemplarycopolymers include those of ethylene/propylene, ethylene/1-butene,ethylene/1-hexane, and ethylene/1-octene and the like. The major portionof such copolymers is derived from ethylene and generally consists ofabout 80-99, preferably 95-99 mole percent of ethylene. These polymersare well suited for extrusion, blow molding, injection molding and thelike.

The polymerization reaction can be conducted by contacting monomer ormonomers, e.g., ethylene, alone or with one or more other olefins, andin the substantial absence of catalyst poisons such as moisture and air,with a catalytic amount of the supported organometallic catalyst at atemperature and at a pressure sufficient to initiate the polymerizationreaction. If desired, an inert organic solvent may be used as a diluentand to facilitate materials handling if the polymerization reaction isconducted with the reactants in the liquid phase, e.g. in a particleform (slurry) or solution process. The reaction may also be conductedwith reactants in the vapor phase, e.g., in a fluidized bed arrangementin the absence of a solvent but, if desired, in the presence of an inertgas such as nitrogen.

The polymerization reaction is carried out at temperatures of from about30° C. or less, up to about 200° C. or more, depending to a great extenton the operating pressure, the pressure of the olefin monomers, and theparticular catalyst being used and its concentration. Naturally, theselected operating temperature is also dependent upon the desiredpolymer melt index since temperature is definitely a factor in adjustingthe molecular weight of the polymer. Preferably, the temperature used isfrom about 30° C. to about 100° C. in a conventional slurry or “particleforming” process or from 100° C. to 150° C. in a “solution forming”process. A temperature of from about 70° C. to 110° C. can be employedfor fluidized bed processes.

The pressure to be used in the polymerization reactions can be anypressure sufficient to initiate the polymerization of the monomer(s) tohigh molecular weight polymer. The pressure, therefore, can range fromsubatmospheric pressures, using an inert gas as diluent, tosuperatmospheric pressures of up to about 30,000 psig or more. Thepreferred pressure is from atmospheric (0 psig) up to about 1000 psig.As a general rule, a pressure of 20 to 800 psig is most preferred.

The selection of an inert organic solvent medium to be employed in thesolution or slurry process embodiments of this invention is not toocritical, but the solvent should be inert to the supportedorganometallic catalyst and olefin polymer produced, and be stable atthe reaction temperature used. It is not necessary, however, that theinert organic solvent medium also serve as a solvent for the polymer tobe produced. Among the inert organic solvents applicable for suchpurposes may be mentioned saturated aliphatic hydrocarbons having fromabout 3 to 12 carbon atoms per molecule such as hexane, heptane,pentane, isooctane, purified kerosene and the like, saturatedcycloaliphatic hydrocarbons having from about 5 to 12 carbon atoms permolecule such as cyclohexane, cyclopentane, dimethylcyclopentane andmethylcyclohexane and the like and aromatic hydrocarbons having fromabout 6 to 12 carbon atoms per molecule such as benzene, toluene,xylene, and the like. Particularly preferred solvent media arecyclohexane, pentane, hexane and heptane.

Hydrogen can be introduced into the polymerization reaction zone inorder to decrease the molecular weight of the polymers produced (i.e.,give a much higher Melt Index, Mich.). Partial pressure of hydrogen whenhydrogen is used can be within the range of 5 to 100 psig, preferably 25to 75 psig. The melt indices of the polymers produced in accordance withthe instant invention can range from about 0.1 to about 70 or evenhigher.

More detailed description of suitable polymerization conditionsincluding examples of particle form, solution and fluidized bedpolymerization arrangements are found in Karapinka; U.S. Pat. No.3,709,853; Issued Jan. 9, 1973 and Karol et al; U.S. Pat. No. 4,086,408;Issued Apr. 25, 1978. Both of these patents are incorporated herein byreference.

Hydrotreating

SSZ-56 is useful in a hydrotreating catalyst. During hydrotreatment,oxygen, sulfur and nitrogen present in the hydrocarbonaceous feed isreduced to low levels. Aromatics and olefins, if present in the feed,may also have their double bonds saturated. In some cases, thehydrotreating catalyst and hydrotreating conditions are selected tominimize cracking reactions, which can reduce the yield of the mostdesulfided product (typically useful as a fuel).

Hydrotreating conditions typically include a reaction temperaturebetween 400-900° F. (204-482° C.), preferably 650-850° F. (343-454° C.);a pressure between 500 and 5000 psig (3.5-34.6 Mpa), preferably 1000 to3000 psig (7.0-20.8 MPa); a feed rate (LHSV) of 0.5 hr⁻¹ to 20 hr⁻¹(v/v); and overall hydrogen consumption 300 to 2000 scf per barrel ofliquid hydrocarbon feed (53.4-356 m³ H₂/m³ feed). The hydrotreatingcatalyst will typically be a composite of a Group VI metal or compoundthereof, and a Group VIII metal or compound thereof supported on themolecular sieve of this invention. Typically, such hydrotreatingcatalyst are presulfided.

Catalysts useful for hydrotreating hydrocarbon feeds are disclosed inU.S. Pat. No. 4,347,121, issued Aug. 31, 1982 to Mayer et al, and U.S.Pat. No. 4,810,357, issued Mar. 7, 1989 to Chester et al, both of whichare incorporated herein by reference in their entirety. Suitablecatalysts include noble metals from Group VIII, such as Fe, Co, Ni, Ptor Pd, and/or Group VI metals, such as Cr, Mo, Sn or W. Examples ofcombinations of Group VIII and Group VI metals include Ni—Mo or Ni—Sn.Other suitable catalysts are described in U.S. Pat. No. 4,157,294,issued Jun. 5, 1979 to Iwao et al, and U.S. Pat. No. 3,904,513, issuedSep. 9, 1975 to Fischer et al. U.S. Pat. No. 3,852,207, issued Dec. 3,1974 to Strangeland et al, describes suitable noble metal catalysts andmild hydrotreating conditions. The contents of these patents are herebyincorporated by reference.

The amount of hydrogenation component(s) in the catalyst suitably rangefrom about 0.5% to about 10% by weight of Group VIII component(s) andfrom 5% to about 25% by weight of Group VI metal component(s),calculated as metal oxide(s) per 100 parts by weight of total catalyst.,where the percentages by weight are based on the weight of the catalystbefore sulfiding. The hydrogenation component(s) in the catalyst may bein the oxidic and/or sulfidic form.

Hydrogenation

SSZ-56 can be used in a catalyst to catalyze hydrogenation of ahydrocarbon feed containing unsaturated hydrocarbons. The unsaturatedhydrocarbons can comprise olefins, dienes, polyenes, aromatic compoundsand the like.

Hydrogenation is accomplished by contacting the hydrocarbon feedcontaining unsaturated hydrocarbons with hydrogen in the presence of acatalyst comprising SSZ-56. The catalyst can also contain one or moremetals of Group VIB and Group VIII, including salts, complexes andsolutions thereof. Reference to these catalytically active metals isintended to encompass such metals or metals in the elemental state or insome form such as an oxide, sulfide, halide, carboxylate and the like.Examples of such metals include metals, salts or complexes wherein themetal is selected from the group consisting of platinum, palladium,rhodium, iridium or combinations thereof, or the group consisting ofnickel, molybdenum, cobalt, tungsten, titanium, chromium, vanadium,rhenium, manganese and combinations thereof.

The hydrogenation component of the catalyst (i.e., the aforementionedmetal) is present in an amount effective to provide the hydrogenationfunction of the catalyst, preferably in the range of from 0.05 to 25% byweight.

Hydrogenation conditions, such as temperature, pressure, spacevelocities, contact time and the like are well known in the art.

EXAMPLES

The following examples demonstrate but do not limit the presentinvention.

Example 1 Synthesis of the Directing agentN,N-Diethyl-2-Methyldecahydroquinolinium Hydroxide

The parent amine 2-Methyldecahydroquinoline was obtained byhydrogenation of 2-methylquinoline (quinaldine) as described below. A1000-ml stainless steel hydrogenation vessel was charged with 200 gm(1.4 mol) of 2-methylquinoline (quinaldine), purchased from AldrichChemical Company, and 300 ml glacial acetic acid, 10 gm of PtO₂ and 15ml concentrated H₂SO₄. The mixture was purged twice with nitrogen (thevessel was pressurized with nitrogen to 1000 psi and evacuated). Then,the reaction vessel was pressurized to 1500-psi of hydrogen gas andallowed to stir at 50° C. overnight. The pressure dropped overnight andthe vessel was pressurized back to 1500 psi (with H₂ gas) and let tostir until no further drop in the pressure was observed. Once thereaction was complete, the mixture was filtered and the filtrate wastreated with 50 wt % aqueous sodium hydroxide solution until a pH of ˜9was achieved. The treated filtrate was diluted with 1000 ml diethylether. The organic layer was separated, washed with water and brine, anddried over anhydrous MgSO₄. Concentration under vacuum (using rotaryevaporator) gave the amine as a pair of isomers (cis-fused andtrans-fused ring system with the methyl group in the equatorial positionin both isomers) in 97% yield (208 gm) in a ratio of 1.1:0.9trans-fused:cis-fused. The authenticity of the product was establishedby spectral data analysis including NMR, IR and GCMS spectroscopy. Inprinciple, there are four likely isomers, but only two isomers wereproduced.

N-Ethyl-2-methyldecahydroquinolinium hydroiodide was prepared accordingto the method described below. To a solution 100 gm (0.65 mol) of2-methyldecahydroquinoline (trans and cis) in 350 ml acetonitrile, 111gm (0.72 mole) of ethyl iodide was added. The mixture was stirred (usingan overhead stirrer) at room temperature for 96 hours. Then, anadditional ½ mole equivalent of ethyl iodide was added and the mixturewas heated at reflux for 6 hours. The reaction mixture was concentratedon a rotary evaporator at reduced pressure and the obtained solids wererinsed with 500 ml ethyl ether to remove any unreactive amines andexcess iodide. The reaction afforded a mixture of twoN-ethyl-2-methyl-decahydroquinolinium hydroiodide salts (mono-ethylderivatives) and a small mixture of the quaternized derivatives. Theproducts were isolated by recrystallization from isopropyl alcoholseveral times to give the pure trans-fused ringN-ethyl-2-methyl-decahydroquinolinium hydroiodide and the pure cis-fusedring N-ethyl-2-methyl-decahydroquinolinium hydroiodide (see the schemebelow).

N,N-Diethyl-2-methyldecahydroquinolinium iodide was prepared accordingto the procedure shown below. The procedure below is typical for makingthe N,N-diethyl-2-methyl-decahydro-quinolinium iodide. The obtainedtransfused ring N-ethyl-2-methyl-decahydroquinolinium hydroiodide (28gm, 0.09 mol) was added to an acetonitrile (150 ml) and KHCO₃ (14 gm,0.14 mol) solution. To this solution, 30 gm (0.19 mol) of ethyl iodidewas added and the resulting mixture was stirred (with an overheadstirrer) at room temperature for 72 hours. Then, one more moleequivalent of ethyl iodide was added and the reaction was heated toreflux and allowed to stir at the reflux temperature for 6 hours.Heating was stopped and the reaction was allowed to further stir at roomtemperature overnight. The reaction was worked up by removing the excessethyl iodide and the solvent at reduced pressure on a rotary evaporator.The resulting solids were suspended in 500 ml chloroform, whichdissolves the desired product and leaves behind the unwanted KHCO₃ andits salt by-products. The solution was filtered, and the filtrate wasdried over anhydrous MgSO₄. Filtration followed by concentration atreduced pressure on a rotary evaporator, gave the desiredN,N-diethyl-2-methyl-decahydroquinolinium iodide as a pale tan-coloredsolid. The solid was further purified by recrystallization in isopropylalcohol. The reaction afforded 26.8 gm (87% yield). TheN,N-diethyl-2-methyl-decahydro-quinolinium iodide of the cis-fused ringisomer was made according to the procedure described above. Thetrans-fused ring derivative A (see the scheme 1 below) is the templatingagent (SDA) useful for making SSZ-56.

N,N-Diethyl-2-methyldecahydroquinolinium hydroxide

The hydroxide version of N,N-diethyl-2-methyldecahydro-quinoliniumcation was prepared by ion exchange as described in the procedure below.To a solution of 20 gm (0.06 mol) ofN,N-diethyl-2-methyldecahydro-quinolinium iodide in 80 ml water, 80 gmof OH-ion exchange resin (BIO RAD® AGI-X8) was added, and the resultingmixture was allowed to gently stir at room temperature for few hours.The mixture was filtered and the ion exchange resin was rinsed withadditional 30 ml water (to ensure removing all the cations from theresin). The rinse and the original filtrate were combined and titrationanalysis on a small sample of the filtrate with 0.1 N HCl indicated a0.5M OH ions concentration (0.055 mol cations). Scheme 1 below depictsthe synthesis of the templating agent.

There are 4 possible isomers (depicted below) from the synthesis, butonly two isomers were produced: trans-fused-equatorial methyl A andcis-fused-equatorial methyl B.

Example 2 Synthesis of Borosilicate SSZ-56 from Calcined Boron-BETAZeolite

In a 23 cc Teflon liner, 3 gm of 0.5M solution (1.5 mmol) ofN,N-diethyl-2-methyldecahydroquinolinium hydroxide (the trans-fused ringisomer), 0.5 gm of 1.0N solution of aqueous NaOH (0.5 mmol), 4.5 gm ofde-ionized water, and 0.65 gm of calcined boron-BETA zeolite were allmixed. The Teflon liner was capped and placed in a Parr reactor andheated in an oven at 150° C. while tumbling at about 43 rpm. Thereaction progress was checked by monitoring the gel's pH and by lookingfor crystal formation using Scanning Electron Microscopy (SEM) at 3-6days intervals. The reaction was usually completed after heating for18-24 days (shorter crystallization periods were achieved at 160° C.).The final pH at the end of the reaction ranged from 10.8-11.6. Once thecrystallization was completed (by SEM analysis), the reaction mixture(usually a white fine powdery precipitate with clear liquid) wasfiltered. The collected solids were rinsed a few times with de-ionizedwater (˜1000 ml), and then let to air-dry overnight followed by dryingin an oven at 120° C. for 15-20 minutes. The reaction yielded about 0.55-0.6 gm of pure boron-SSZ-56 as determined by XRD analysis.

Example 3 Seeded Preparation of Borosilicate SSZ-56

In a 23 cc Teflon liner, 3 gm of 0.5M solution (1.5 mmol) ofN,N-diethyl-2-methyldecahydroquinolinium hydroxide (the trans-fused ringisomer), 0.5 gm of 1.0N solution of aqueous NaOH (0.5 mmol), 4.5 gm ofde-ionized water, 0.65 gm of calcined boron-BETA zeolite and 0.03 gm ofSSZ-56 (made as described above) were mixed. The Teflon liner was cappedand placed in a Parr reactor and heated in an oven at 150° C. whiletumbling at about 43 rpm. The reaction progress was checked bymonitoring the gel's pH and by looking for crystal formation usingScanning Electron Microscopy (SEM) at 3 day intervals. Thecrystallization was complete (SEM analysis) after heating for 6 days.The final pH at the end of the reaction was usually 11.2. Oncecompleted, the reaction mixture was filtered, and the collected solidswere rinsed with de-ionized water (˜1000 ml), and then let to air-dryovernight followed by drying in an oven at 120° C. for 15-20 minutes.The reaction yielded 0.6 gm of pure boron-SSZ-56. Identity andcharacterization of the material was determined by XRD analysis.

Example 4 Direct Synthesis of Borosilicate SSZ-56 from Sodium BorateDecahydrate as the Boron Sources and CAB-O-SIL M-5 as the Silicon Source

In a 23 cc Teflon liner, 6 gm of 0.5M solution (3 mmol) ofN,N-diethyl-2-methyldecahydroquinolinium hydroxide (the trans-fused ringisomer), 1.2 gm of 1.0N solution of aqueous NaOH (1.2 mmol), 4.8 gm ofde-ionized water, and 0.065 gm of sodium borate decahydrate were mixedand stirred until the sodium borate was completely dissolved. Then, 0.9gm of Cab-O-Sil M-5 (˜98% SiO2) was added and thoroughly mixed. Theresulting gel was capped and placed in a Parr reactor and heated in anoven at 160° C. while tumbling at about 43 rpm. The reaction progresswas checked by monitoring the gel's pH and by looking for crystalformation using Scanning Electron Microscopy (SEM) at 6 days intervals.The reaction was usually completed after heating for 18-24 days. Thefinal pH at the end of the reaction ranged from 11.5-12.3. Once thecrystallization was completed (by SEM analysis), the reaction mixture, awhite fine powdery precipitate with clear liquid, was filtered. Thecollected solids were rinsed few times with de-ionized water (˜1000 ml),and then air-dried overnight followed by drying in an oven at 120° C.for 15 minutes. The reaction usually yields about 0.75-0.9 gm of pureboron-SSZ-56.

Example 5 Seeded Synthesis of Borosilicate SSZ-56 from Sodium BorateDecahydrate as the Boron Source and CAB-O-SIL M-5 as the Silicon Source

In a 23 cc Teflon liner, 6 gm of 0.5M solution (3 mmol) ofN,N-diethyl-2-methyldecahydroquinolinium hydroxide (the trans-fused ringisomer), 1.2 gm of 1.0N solution of aqueous NaOH (1.2 mmol), 4.8 gm ofde-ionized water, and 0.062 gm of sodium borate decahydrate were mixedand stirred until the sodium borate was completely dissolved. Then, 0.9gm of Cab-O-Sil M-5 (˜98% SiO2) and 0.04 gm of B-SSZ-56 made as inExample 4 were added and thoroughly mixed. The resulting gel was cappedand placed in a Parr reactor and heated in an oven at 160° C. whiletumbling at about 43 rpm. The reaction progress was checked bymonitoring the gel's pH and by looking for crystal formation usingScanning Electron Microscopy (SEM) at 3-5 days intervals. The reactionwas completed after heating for 7 days. The final pH at the end of thereaction was about 12.2. Once the crystallization was completed (by SEManalysis), the reaction mixture, a white fine powdery precipitate withclear liquid, was filtered. The collected solids were rinsed few timeswith de-ionized water (˜1000 ml), and then air-dried overnight followedby drying in an oven at 120° C. for 15 minutes. The reaction yielded0.88 gm of pure boron-SSZ-56.

Example 6 Calcination of SSZ-56

Removing the templating agent molecules (structure-directing agents:SDAs) from zeolite SSZ-56 to free its channels and cavities wasaccomplished by the calcination method described below. A sample of theas-made SSZ-56 synthesized according to the procedures of Examples 2, 3,4 or 5 discussed above is calcined by preparing a thin bed of SSZ-56 ina calcination dish which was heated in a muffle furnace from roomtemperature to 595° C. in three stages. The sample was heated to120° C.at a rate of 1° C./minute and held for 2 hours. Then, the temperaturewas ramped up to 540° C. at a rate of 1° C./minute and held for 5 hours.The temperature was then ramped up again at 1° C./minute to 595° C. andheld there for 5 hours. A nitrogen stream with a slight bleed of air waspassed over the zeolite at a rate of 20 standard cubic feet (0.57standard cubic meters) per minute during heating the calcinationprocess.

Example 7 Ammonium-Ion Exchange of SSZ-56

The Na⁺ form of SSZ-56 prepared as in Examples 2, 3, 4 or 5 and calcinedas in Example 6 was converted to NH₄+-SSZ-56 form by heating thematerial in an aqueous solution of NH₄NO₃ (typically 1 gm NH₄NO₃/1 gmSSZ-56 in 20 ml H₂O) at 90° C. for 2-3 hours. The mixture was thenfiltered and the step was repeated as many times as desired (usuallydone 2-3 times). After filtration, the obtained NH₄-exchanged-productwas washed with de-ionized water and air dried. The NH₄ ⁺ form of SSZ-56can be converted to the H⁺ form by calcination to 540° C. (as describedin Example 6 above stopping at the end of the second stage).

Example 8 Preparation of Aluminosilicate SSZ-56 by Aluminum Exchange ofBoron-SSZ-56

The aluminosilicate version of SSZ-56 was prepared by way of exchangingborosilicate SSZ-56 with aluminum nitrate according to the proceduredescribed below. The H⁺ version of calcined borosilicate SSZ-56(prepared as in Examples 2, 3, 4 or 5 and treated with ammonium nitrateand calcined as Example 6) was easily converted to the aluminosilicateSSZ-56 by suspending the zeolite (H⁺/borosilicate SSZ-56) in 1 Msolution of aluminum nitrate nonahydrate (10 ml of 1M Al(NO₃)₃.9H₂Osoln./1 gm SSZ-56). The suspension was heated at reflux overnight. Theresulting mixture was then filtered and the collected solids werethoroughly rinsed with de-ionized water and air-dried overnight. Thesolids were further dried in an oven at 120° C. for 2 hours. Theexchange can also be done on the Na⁺ version of SSZ-56 (as prepared inExamples 2, 3, 4 or 5 and calcined as in Example 6).

Example 9 Nitrogen Adsorption (MicroPore Volume Analysis)

The Na⁺ and H⁺ forms of SSZ-56 as synthesized in Examples 2 and 4 aboveand treated as in Examples 6 and 7 was subjected to a surface area andmicropore volume analysis using N₂ as adsorbate and via the BET method.The zeolite exhibited a considerable void volume with a micropore volumeof 0.18 cc/g for Na⁺ form, and 0.19 cc/gm for the H⁺ form.

Example 10 Argon Adsorption (MicroPore Volume Analysis)

A calcined sample of Na⁺ version of borosilicate SSZ-56 (synthesized asin Example 2 and calcined as in Example 6) had a micropore volume of0.16 cc/gm based on argon adsorption isotherm at 87.50 K (−186° C.)recorded on ASAP 2010 equipment from Micromerities. The sample was firstdegassed at 400° C. for 16 hours prior to argon adsorption. Thelow-pressure dose was 2.00 cm3/g (STP). A maximum of one hourequilibration time per dose was used and the total run time was 37hours. The argon adsorption isotherm was analyzed using the densityfunction theory (DFT) formalism and parameters developed for activatedcarbon slits by Olivier (Porous Mater. 1995, 2, 9) using the Saito Foleyadaptation of the Horvarth-Kawazoe formalism (Microporous Materials,1995, 3, 531) and the conventional t-plot method (J. Catalysis, 1965, 4,319).

Example 11 Constraint Index Test

The hydrogen form of SSZ-56 synthesized as in Example 2 was calcined andammonium exchanged as in Examples 6 and 7 was aluminum exchanged as inExample 8. The obtained aluminum-exchanged sample of SSZ-56 was thenammonium exchanged as in Example 7 followed by calcination to 540° C. asin Example 6. The H-Al-SSZ-56 was pelletized at 4 KPSI, crushed andgranulated to 20-40 mesh. A 0.6 gram sample of the granulated materialwas calcined in air at 540° C. for 4 hours and cooled in a desiccator toensure dryness. Then, 0.5 gram was packed into a ⅜ inch stainless steeltube with alundum on both sides of the molecular sieve bed. A Lindburgfurnace was used to heat the reactor tube. Helium was introduced intothe reactor tube at 10 cc/min. and at atmospheric pressure. The reactorwas heated to about 315° C., and a 50/50 feed of n-hexane and3-methylpentane is introduced into the reactor at a rate of 8 μl/min.The feed was delivered by a Brownlee pump. Direct sampling into a GCbegan after 10 minutes of feed introduction. The Constraint Index (CI)value was calculated from the GC data using methods known in the art.SSZ-56 had a Cl of 0.76 and a conversion of 79% after 15 minutes onstream. The material fouled rapidly and at 105 minutes the Cl was 0.35and the conversion was 25.2%. The Cl test showed the material was veryactive catalytic material.

Example 12 n-Hexadecane Hydrocracking Test

A 1 gm sample of SSZ-56 (prepared as described for the Constraint Indextest in Example 11) was suspended in 10 gm de-ionized water. To thissuspension, a solution of Pd(NH₃)₄(NO₃)₂ at a concentration which wouldprovide 0.5 wt. % Pd with respect to the dry weight of the molecularsieve sample was added. The pH of the solution was adjusted to pH of 9.2by a drop-wise addition of 0.15N solution of ammonium hydroxide. Themixture was then heated in an oven at 75° C. for 48 hours. The mixturewas then filtered through a glass frit, washed with de-ionized water,and air-dried. The collected Pd-SSZ-56 sample was slowly calcined up to482° C. in air and held there for three hours.

The calcined Pd/SSZ-56 catalyst was pelletized in a Carver Press andgranulated to yield particles with a 20/40 mesh size. Sized catalyst(0.5 g) was packed into a ¼ inch OD tubing reactor in a micro unit forn-hexadecane hydroconversion. The table below gives the run conditionsand the products data for the hydrocracking test on n-hexadecane.

As the results show in the table below, SSZ-56 is a very active andisomerisation selective catalyst at 96.5% n-C₁₆ conversion at 256° C.Temperature 256° C. (496° F.) Time-on-Stream (hrs.) 71.4-72.9 WHSV 1.55PSIG 1200 Titrated? NO n-16, % Conversion 96.5 Hydrocracking Conv. 35.2Isomerization Selectivity, % 63.5 Cracking Selectivity, % 36.5 C⁴⁻ % 2.3C₅/C₄ 15.2 C₅₊C₆/C₅, % 19.3 DMB/MP 0.05 C₄-C₁₃ i/n 3.7 C₇-C₁₃ yield 27.7

1. A process for converting hydrocarbons comprising contacting ahydrocarbonaceous feed at hydrocarbon converting conditions with acatalyst comprising a molecular sieve having a mole ratio greater thanabout 15 of (1) an oxide of a first tetravalent element to (2) an oxideof a trivalent element, pentavalent element, second tetravalent elementwhich is different from said first tetravalent element or mixturethereof and having, after calcination, the X-ray diffraction lines ofTable
 2. 2. The process of claim 1 wherein the molecular sieve ispredominantly in the hydrogen form.
 3. The process of claim 1 whereinthe molecular sieve is substantially free of acidity.
 4. The process ofclaim 1 wherein the process is a hydrocracking process comprisingcontacting the catalyst with a hydrocarbon feedstock under hydrocrackingconditions.
 5. The process of claim 4 wherein the molecular sieve ispredominantly in the hydrogen form.
 6. The process of claim 1 whereinthe process is a dewaxing process comprising contacting the catalystwith a hydrocarbon feedstock under dewaxing conditions.
 7. The processof claim 6 wherein the molecular sieve is predominantly in the hydrogenform.
 8. The process of claim 1 wherein the process is a process forimproving the viscosity index of a dewaxed product of waxy hydrocarbonfeeds comprising contacting the catalyst with a waxy hydrocarbon feedunder isomerization dewaxing conditions.
 9. The process of claim 8wherein the molecular sieve is predominantly in the hydrogen form. 10.The process of claim 1 wherein the process is a process for producing aC₂₀₊ lube oil from a C₂₀₊ olefin feed comprising isomerizing said olefinfeed under isomerization conditions over the catalyst.
 11. The processof claim 10 wherein the molecular sieve is predominantly in the hydrogenform.
 12. The process of claim 10 wherein the catalyst further comprisesat least one Group VIII metal.
 13. The process of claim 1 wherein theprocess is a process for catalytically dewaxing a hydrocarbon oilfeedstock boiling above about 350° F. (177° C.) and containing straightchain and slightly branched chain hydrocarbons comprising contactingsaid hydrocarbon oil feedstock in the presence of added hydrogen gas ata hydrogen pressure of about 15-3000 psi (0.103-20.7 MPa) under dewaxingconditions with the catalyst.
 14. The process of claim 13 wherein themolecular sieve is predominantly in the hydrogen form.
 15. The processof claim 13 wherein the catalyst further comprises at least one GroupVIII metal.
 16. The process of claim 13 wherein said catalyst comprisesa layered catalyst comprising a first layer comprising the molecularsieve and at least one Group VIII metal, and a second layer comprisingan aluminosilicate zeolite which is more shape selective than themolecular sieve of said first layer.
 17. The process of claim 1 whereinthe process is a process for preparing a lubricating oil whichcomprises: hydrocracking in a hydrocracking zone a hydrocarbonaceousfeedstock to obtain an effluent comprising a hydrocracked oil; andcatalytically dewaxing said effluent comprising hydrocracked oil at atemperature of at least about 400° F. (204° C.) and at a pressure offrom about 15 psig to about 3000 psig (0.103 to 20.7 MPa gauge) in thepresence of added hydrogen gas with the catalyst.
 18. The process ofclaim 17 wherein the molecular sieve is predominantly in the hydrogenform.
 19. The process of claim 17 wherein the catalyst further comprisesat least one Group VIII metal.
 20. The process of claim 1 wherein theprocess is a process for isomerization dewaxing a raffinate comprisingcontacting said raffinate in the presence of added hydrogen underisomerization dewaxing conditions with the catalyst.
 21. The process ofclaim 20 wherein the molecular sieve is predominantly in the hydrogenform.
 22. The process of claim 20 wherein the catalyst further comprisesat least one Group VIII metal.
 23. The process of claim 20 wherein theraffinate is bright stock.
 24. The process of claim 1 wherein theprocess is a process for increasing the octane of a hydrocarbonfeedstock to produce a product having an increased aromatics contentcomprising contacting a hydrocarbonaceous feedstock which comprisesnormal and slightly branched hydrocarbons having a boiling range aboveabout 40° C. and less than about 200° C. under aromatic conversionconditions with the catalyst.
 25. The process of claim 24 wherein themolecular sieve is substantially free of acid.
 26. The process of claim24 wherein the molecular sieve contains a Group VIII metal component.27. The process of claim 1 wherein the process is a catalytic crackingprocess comprising contacting a hydrocarbon feedstock in a reaction zoneunder catalytic cracking conditions in the absence of added hydrogenwith the catalyst.
 28. The process of claim 27 wherein the molecularsieve is predominantly in the hydrogen form.
 29. The process of claim 27wherein the catalyst additionally comprises a large pore crystallinecracking component.
 30. The process of claim 1 wherein the process is anisomerization process for isomerizing C₄ to C₇ hydrocarbons, comprisingcontacting a feed having normal and slightly branched C₄ to C₇hydrocarbons under isomerizing conditions with the catalyst.
 31. Theprocess of claim 30 wherein the molecular sieve is predominantly in thehydrogen form.
 32. The process of claim 30 wherein the molecular sievehas been impregnated with at least one Group VIII metal.
 33. The processof claim 30 wherein the catalyst has been calcined in a steam/airmixture at an elevated temperature after impregnation of the Group VIIImetal.
 34. The process of claim 32 wherein the Group VIII metal isplatinum.
 35. The process of claim 1 wherein the process is a processfor alkylating an aromatic hydrocarbon which comprises contacting underalkylation conditions at least a molar excess of an aromatic hydrocarbonwith a C₂ to C₂₀ olefin under at least partial liquid phase conditionsand in the presence of the catalyst.
 36. The process of claim 35 whereinthe molecular sieve is predominantly in the hydrogen form.
 37. Theprocess of claim 35 wherein the olefin is a C₂ to C₄ olefin.
 38. Theprocess of claim 37 wherein the aromatic hydrocarbon and olefin arepresent in a molar ratio of about 4:1 to about 20:1, respectively. 39.The process of claim 37 wherein the aromatic hydrocarbon is selectedfrom the group consisting of benzene, toluene, ethylbenzene, xylene,naphthalene, naphthalene derivatives, dimethylnaphthalene or mixturesthereof.
 40. The process of claim 1 wherein the process is a process fortransalkylating an aromatic hydrocarbon which comprises contacting undertransalkylating conditions an aromatic hydrocarbon with a polyalkylaromatic hydrocarbon under at least partial liquid phase conditions andin the presence of the catalyst.
 41. The process of claim 40 wherein themolecular sieve is predominantly in the hydrogen form.
 42. The processof claim 40 wherein the aromatic hydrocarbon and the polyalkyl aromatichydrocarbon are present in a molar ratio of from about 1:1 to about25:1, respectively.
 43. The process of claim 40 wherein the aromatichydrocarbon is selected from the group consisting of benzene, toluene,ethylbenzene, xylene, or mixtures thereof.
 44. The process of claim 40wherein the polyalkyl aromatic hydrocarbon is a dialkylbenzene.
 45. Theprocess of claim 1 wherein the process is a process to convert paraffinsto aromatics which comprises contacting paraffins under conditions whichcause paraffins to convert to aromatics with a catalyst comprising themolecular sieve and gallium, zinc, or a compound of gallium or zinc. 46.The process of claim 1 wherein the process is a process for isomerizingolefins comprising contacting said olefin under conditions which causeisomerization of the olefin with the catalyst.
 47. The process of claim1 wherein the process is a process for isomerizing an isomerization feedcomprising an aromatic C₈ stream of xylene isomers or mixtures of xyleneisomers and ethylbenzene, wherein a more nearly equilibrium ratio ofortho-, meta and para-xylenes is obtained, said process comprisingcontacting said feed under isomerization conditions with the catalyst.48. The process of claim 1 wherein the process is a process foroligomerizing olefins comprising contacting an olefin feed underoligomerization conditions with the catalyst.
 49. A process forconverting oxygenated hydrocarbons comprising contacting said oxygenatedhydrocarbon under conditions to produce liquid products with a catalystcomprising a molecular sieve having a mole ratio greater than about 15of an oxide of a first tetravalent element to an oxide of a secondtetravalent element which is different from said first tetravalentelement, trivalent element, pentavalent element or mixture thereof andhaving, after calcination, the X-ray diffraction lines of Table
 2. 50.The process of claim 49 wherein the oxygenated hydrocarbon is a loweralcohol.
 51. The process of claim 50 wherein the lower alcohol ismethanol.
 52. The process of claim 1 wherein the process is a processfor the production of higher molecular weight hydrocarbons from lowermolecular weight hydrocarbons comprising the steps of: (a) introducinginto a reaction zone a lower molecular weight hydrocarbon-containing gasand contacting said gas in said zone under C₂₊ hydrocarbon synthesisconditions with the catalyst and a metal or metal compound capable ofconverting the lower molecular weight hydrocarbon to a higher molecularweight hydrocarbon; and (b) withdrawing from said reaction zone a highermolecular weight hydrocarbon-containing stream.
 53. The process of claim52 wherein the metal or metal compound comprises a lanthanide oractinide metal or metal compound.
 54. The process of claim 52 whereinthe lower molecular weight hydrocarbon is methane.
 55. A catalystcomposition for promoting polymerization of 1-olefins, said compositioncomprising (A) a molecular sieve having a mole ratio greater than about15 of (1) an oxide of a first tetravalent element to (2) an oxide of atrivalent element, pentavalent element, second tetravalent element whichis different from said first tetravalent element or mixture thereof andhaving, after calcination, the X-ray diffraction lines of Table 2; and(B) an organotitanium or organochromium compound.
 56. The catalystcomposition of claim 55 wherein oxide (1) is silicon oxide, and oxide(2) is an oxide selected from aluminum oxide, gallium oxide, iron oxide,boron oxide, titanium oxide, indium oxide.
 57. The process of claim 1wherein the process is a process for polymerizing 1-olefins, whichprocess comprises contacting 1-olefin monomer with a catalyticallyeffective amount of a catalyst composition comprising (A) a molecularsieve having a mole ratio greater than about 15 of (1) an oxide of afirst tetravalent element to (2) an oxide of a trivalent element,pentavalent element, second tetravalent element which is different fromsaid first tetravalent element or mixture thereof and having, aftercalcination, the X-ray diffraction lines of Table 2; and (B) anorganotitanium or organochromium compound under polymerizationconditions which include a temperature and pressure suitable forinitiating-and promoting the polymerization reaction.
 58. The process ofclaim 57 wherein oxide (1) is silicon oxide, and oxide (2) is an oxideselected from aluminum oxide, gallium oxide, iron oxide, boron oxide,titanium oxide, indium oxide.
 59. The process of claim 57 wherein the1-olefin monomer is ethylene.
 60. The process of claim 58 wherein the1-olefin monomer is ethylene.
 61. The process of claim 1 wherein theprocess is a process for hydrogenating a hydrocarbon feed containingunsaturated hydrocarbons, the process comprising contacting the feedwith hydrogen under conditions which cause hydrogenation with thecatalyst.
 62. The process of claim 61 wherein the catalyst containsmetals, salts or complexes wherein the metal is selected from the groupconsisting of platinum, palladium, rhodium, iridium or combinationsthereof, or the group consisting of nickel, molybdenum, cobalt,tungsten, titanium, chromium, vanadium, rhenium, manganese andcombinations thereof.
 63. A process for hydrotreating a hydrocarbonfeedstock comprising contacting the feedstock with a hydrotreatingcatalyst and hydrogen under hydrotreating conditions, wherein thecatalyst comprises a molecular sieve having a mole ratio greater thanabout 15 of (1) an oxide of a first tetravalent element to (2) an oxideof a trivalent element, pentavalent element, second tetravalent elementwhich is different from said first tetravalent element or mixturethereof and having, after calcination, the X-ray diffraction lines ofTable
 2. 64. The process of claim 63 wherein the catalyst contains aGroup VIII metal or compound, a Group VI metal or compound orcombinations thereof.
 65. A process for hydrotreating a hydrocarbonfeedstock comprising contacting the feedstock with a hydrotreatingcatalyst and hydrogen under hydrotreating conditions, wherein thecatalyst comprises a molecular sieve having a mole ratio greater thanabout 15 of (1) an silicon oxide (2) an oxide selected from aluminumoxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indiumoxide and mixtures thereof, and having, after calcination, the X-raydiffraction lines of Table
 2. 66. The process of claim 65 wherein theoxides comprise silicon oxide and aluminum oxide.
 67. The process ofclaim 65 wherein the oxides comprise silicon oxide and boron oxide. 68.The process of claim 65 wherein the oxide comprises silicon oxide. 69.The process of claim 65 wherein the catalyst contains a Group VIII metalor compound, a Group VI metal or compound or combinations thereof.
 70. Aprocess for converting hydrocarbons comprising contacting ahydrocarbonaceous feed at hydrocarbon converting conditions with acatalyst comprising a molecular sieve having a mole ratio greater thanabout 15 of (1) silicon oxide to (2) an oxide selected from aluminumoxide, gallium oxide, iron oxide, boron oxide, titanium oxide, indiumoxide and mixtures thereof, and having, after calcination, the X-raydiffraction lines of Table 2.